EP0033417B1 - Procédé et composition pour l'inhibition de la corrosion - Google Patents

Procédé et composition pour l'inhibition de la corrosion Download PDF

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Publication number
EP0033417B1
EP0033417B1 EP80304433A EP80304433A EP0033417B1 EP 0033417 B1 EP0033417 B1 EP 0033417B1 EP 80304433 A EP80304433 A EP 80304433A EP 80304433 A EP80304433 A EP 80304433A EP 0033417 B1 EP0033417 B1 EP 0033417B1
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Prior art keywords
water
composition
corrosion
orthophosphate
polymer
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German (de)
English (en)
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EP0033417A1 (fr
Inventor
Roger Cletus May
Gary Edwin Geiger
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BetzDearborn Europe Inc
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Betz Europe Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/105—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • C02F5/125—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen combined with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus

Definitions

  • the most widely used non-chromate treatments are based on polyphosphate.
  • the treatment programs patented by Gaupp (U.S. Patent 3,992,318) and Hollingshad (U.S. Patent 3,941,562) represent these conventional phosphate-based corrosion control programs which prevent corrosion through the formation of an oxygen diffusion barrier film.
  • Polyphosphates provide corrosion protection through an electrodeposition mechanism that results in a calcium phosphate film on the metal surface. (See Drew, Principles of Industrial Water Treatment, pages 62, 63). This film physically separates the metal surface from the aqueous medium and prevents dissolved oxygen from reaching the metal surface, thereby preventing corrosion.
  • the conventional phosphate-based programs suffer from the fact that they derive their corrosion inhibiting properties from a barrier film (deposit).
  • the DE-A-26 43 422 is directed to a water treatment agent and its use for preventing the formation of corrosion, scale and contamination on the surface of the metal that is in contact with the water.
  • the invention of this publication lies in a specific polymer containing a structural unit that is derived from a monomer having an ethylenically unsaturated bond and which has one or more carboxyl radicals, at least a part of said carboxyl radicals being modified.
  • the polymer must contain the groupings represented by the formulas: where OA is an oxyalkylene having 2 to 4 carbon atoms and X is an hydroxyl radical, an alkoxy radical having 1 to 4 carbon atoms or a monovalent phosphate radical, X 1 is a divalent phosphate radical, and a is a positive integer.
  • the polymer may be combined with a whole host of other conventional water treating agents including but not limited to polyphosphoric acids, phosphonic acids, orthophosphoric acid, polyvalent metal salts such as zinc and nickel salts, or organic phosphoric esters.
  • agents may be used in conjunction with chromates, bichromates, tungstates, molybdates, benzotriazole, mercaptobenzothiazole, etc.
  • agents may be used such as lignin derivatives, tannic acids, starch, polyacrylic soda, polyacrylic amide, as well as metal ion sequestering agents such as ethylene diamine, diethylene triamine, nitrilo triacetic acid, EDTA, and diethylene triamine pentaacetic acid.
  • the polymers may be produced from:
  • the polymers may be homopolymers, copolymers, or terpolymers.
  • the polymers specifically disclosed for the most part are terpolymers composed of optional units such as esters of (meth)acrylic acid such as methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethyl hexyl(meth)acrylate, dimethyl amino(meth)acrylate, diethyl amino ethyl(meth)acrylate, etc.; styrene compounds such as styrene, methyl styrene etc.; fatty acid esters of vinyl alcohols, etc.; etc.
  • Typical of the chromate-free treatments are those specified in Carter and Vogt U.S. Patent 3,837,803.
  • One of the objects of this invention is to improve upon the invention of the above-identified patent.
  • Inorganic phosphates although having the capacity, could not be used effectively.
  • the present inventors after much investigation, have discovered a treatment(s) which has successfully established the much desired but elusive passive oxide film (also believed to be a gamma ferric oxide film) on ferrous-based metallic surfaces in contact with aqueous systems, and in particular cooling water systems.
  • the present inventors discovered that if the aqueous medium contained in or being conveyed by a metallic system was first adjusted to a pH of 5.5 or above, and secondly measured to assure a particular calcium ion content, that the elusive passive oxide film is formed upon the metallic surfaces to thereby protect such from corrosion through the use of a treatment comprising a water-soluble orthophosphate together with a water-soluble polymer composed primarily of units derived from acrylic acid (or its water-soluble salts) and units derived from an hydroxy lower alkyl acrylate. Additional protection is obtained by including in the treatment water-soluble polyphosphates and/or water-soluble organophosphonic acid derivatives (or salts thereof).
  • organophosphonic acid derivatives contemplated for use in accordance with the present invention are those disclosed in columns 5 through 9 of U.S. 3,837,803 and exemplified later below.
  • the polyphosphates operable are those generally used for corrosion inhibition purposes and which will be described more fully later herein.
  • copper corrosion inhibitors such as benzotriazole, mercaptobenzothiazole, mercaptobenzothiol, tolyltriazole or benzothiazole compounds, in the composition or in the treatment.
  • composition for providing a protective passive oxide film on the surface of a ferrous metallic part in contact with an aqueous solution with little or no attendant deposition of scale on said part which comprises
  • the invention also includes a method of inhibiting the corrosion of ferrous metal parts in contact with a zinc-free aqueous solution with little or no attendant deposition of scale on said ferrous parts, which corrosion inhibition is obtained by providing for the formation of a protective passive oxide film on the metal surface in contact with said aqueous medium, which method comprises
  • the water-soluble orthophosphate compounds which are operable for the present purposes generally include phosphoric acid, the sodium orthophosphates, the potassium orthophosphates, the lithium orthophosphates and ammonium orthophosphates.
  • the following specific compounds may be mentioned as exemplary:
  • organic orthophosphates which possess the basic formula: where R is an alkyl radical having 1 to 25 carbon atoms, X is A or R, and A is H, Ha, Li, K or NH 4 . Compounds of the above nature are an excellent source of orthophosphate.
  • AA acrylic acid compound
  • water-soluble cation e.g., NH 4 or alkali metal (K, Na)
  • HAA hydroxylated lower alkyl
  • the polymers are considered, most broadly, to have a mole ratio of AA:HAA of from 1:4 to 36:1. This mole ratio is preferably 1:1 to 11:1, and most preferably 1:1 to 5:1.
  • the only criteria that is considered to be of importance with respect to mole ratios is that it is desirable to have a copolymer which is water-soluble. As the proportion of hydroxylated alkyl acrylate units increases, the solubility of the copolymer decreases. It is noted that, from an efficacy point of view, the polymers having a mole ratio of AA:HAA of 1:1 to 5:1 were considered the best.
  • the polymers could have a molecular weight of from 1,000 to 50,000, with from 2,000 to 6,000 being preferred.
  • a preferred polymer is one in which the hydroxy alkyl acrylate is hydroxyl propyl acrylate. It is also preferred that in such a polymer the ratio of the acrylic acid units to the hydroxyl propyl acrylate units is 3:1 and the polymer has a molecular weight of 6,000.
  • the polymer prepared either by copolymerization of AA with hydroxy propyl acrylate (HPA) or reaction of AA with propylene oxide would be composed of units having the structural formulas: where M is as earlier defined.
  • the water-soluble polyphosphate compounds which are operable for the present purposes generally include the sodium polyphosphates, the potassium polyphosphates, the lithium polyphosphates and ammonium polyphosphates.
  • the following specific compounds may be mentioned as exemplary:
  • any polyphosphate which is known to inhibit corrosion in aqueous systems may be utilized.
  • the organo-phosphonic acid compounds are those having a carbon to phosphorous bond, i.e.,
  • R is a lower alkyl having from one to six carbon atoms, e.g., methyl, ethyl, butyl, propyl, isopropyl, pentyl, isopentyl and hexyl; substituted lower alkyl of from one to six carbon atoms, e.g., hydroxyl and amino-substituted alkyls; a mononuclear aromatic (aryl) radical, e.g.
  • phenyl or benzene or a substituted mononuclear aromatic compound, e.g., hydroxyl, amino, lower alkyl substituted aromatic, e.g., benzyl phosphonic acid; and M is a water-soluble cation, e.g., sodium, potassium, ammonium, lithium, etc. or hydrogen.
  • salts of nickel, cobalt, chromium or cadmium such as for example the chlorides, chlorates, bromides, bromates, borates, nitrates, sulfates, acetates, benzoates, butyrates, carbonates, citrates or caproates may be included in the treatment so long as the salt is water-soluble to an acceptable degree.
  • alkalis such as sodium hydroxide, sodium carbonate, potassium hydroxide or calcium hydroxide may be utilized.
  • the acid or base may be included in the composition containing the orthophosphate compound.
  • compositions containing the polymer (AA/HAA) and the orthophosphate are not particularly stable when mixed as a highly active product for delivery to a user, it is desirable to treat the systems using what the industry considers a two-barrel approach, i.e., feed ingredients separately. Since the polyphosphates, the phosphonates, and the copper corrosion inhibitors, e.g., totylthiazole, mix quite well with the orthophosphate, these are included in one drum when utilized as the treatment. It is possible however, to blend all of the ingredients dry as powder or crystals and make the liquid from at the use sites. Stability is not a significant problem when the make is used within a short time.
  • the invention contemplates the use of a composition containing the polymer and the orthophosphate and optionally but preferably the phosphonate, the polyphosphate and the copper corrosion inhibitors.
  • Any copper corrosion inhibitor may be included in the composition in an amount of 0.01 to 5% by weight of the composition which will be effective for controlling the copper corrosion in a given system by providing 0.05 to 10 parts per million parts of water in the system and preferably .5 to 5 parts per million.
  • the preferred rate of application of this treatment to cooling water systems and the ratios of various components depends on the calcium concentration of the cooling water.
  • the treatment is preferably applied in waters having between 15 ppm and 1,000 ppm calcium. Within this range the weight ratio of calcium to orthophosphate is varied from 1:1 1 to 83.3: 1, the weight ratio of AAIHAA to orthophosphate is varied from 1:3 to 1.5:1.
  • the orthophosphate which is critical to the present inventive treatment is generally obtained by direct addition. However, it is understood that the orthophosphate can also arise due to reversion of either inorganic polyphosphates or the organo-phosphones, or any other appropriate source or precursor thereof.
  • the above dosages represent the most desirable ranges since most systems will be treatable therewith. Higher dosages are permissible when the situation demands, but of course are more costly.
  • the effectiveness of the inventive treatments are dependent upon the aqueous medium having a pH of 5.5 and above, and preferably 6.5 to 9.5, and containing calcium concentrations of 15 parts per million parts of water or above. Below this range, it may be necessary for overall effectiveness to add metallic ions such as zinc, nickel and chromium.
  • test conditions In describing the test conditions the patent makes the following disclosure as pertains to the test conditions:
  • TTA Tolyltriazole
  • Treatments F and G compared the performance of a polyacrylic acid-orthophosphate composition disclosed by Hollingshad with that of an AA/HPA-orthophosphate composition disclosed in the above-identified application.
  • the Hollingshad polyacrylic acid-orthophosphate formulation (Treatment F) provides corrosion protection through the formation of a calcium phosphate barrier film and suffers from the inability to prevent localized deposition and subsequent under deposit corrosion, a common problem with this type treatment.
  • the AAIHPA- orthophosphate treatment (Treatment C) is clearly superior in that it gives lower corrosion rates and does not rely on the formation of a calcium phosphate barrier film.
  • the ability to inhibit steel corrosion with an orthophosphate-based treatment that does not rely on a barrier film to provide corrosion protection was previously unattainable and therefore represents unique and unexpected behaviour.
  • Treatment C A comparison of the performance of Treatments C and H illustrates the similarities between the orthophosphate-based program claimed in the present application (Treatment C) and chromate (Treatment H). Both treatments give nearly identical corrosion rates without formation of a barrier film.
  • the pH and temperature of the bulk water are automatically controlled.
  • the treated water is prepared by chemical addition to deionized water. Provisions for continuous make-up and blowdown are made by pumping fresh treated water from supply tanks to the sump, with overflow from the sump serving as blowdown.
  • Corrosion rates are determined by exposing precleaned and weighed metal specimens for a specified period of time, after which they are removed, cleaned and reweighed. Corrosion rates are calculated by dividing the total coupon weight loss by the number of days of exposure.
  • the lack of deposition is very important since it permits, for example in a cooling water operation, virtually unimpeded flow of the cooling medium with high heat transfer capabilities, prompting a significant cost advantage because of greater efficiency at lower and less expensive energy requirements.
  • Table IX illustrate the unexpected improvement obtained using the present invention in contrast to that of US ⁇ A ⁇ 4,209,398, which does not suggest that if one chooses a particular combination of polymer and phosphate from the vast number of possibilities set forth in its specification that exceptional corrosion protection is obtained in accordance with the criteria of the present invention.
  • the unexpected effectiveness of the present invention is evident from the corrosion data in the Table. Little or no deposition occurs, contrary to the results of US-A-4,209,398. It should also be pointed out that the testing conditions employed in the Table are much more severe than those utilized in the testing procedure of US-A-4,209,398 and accordingly are a better representation of actual commercial conditions generally encountered.
  • a midwestern petrochemical plant was using a conventional phosphate/dispersant program in their open recirculating cooling system to control corrosion.
  • phosphate/dispersant treatment applied at a concentration that would give 3 ppm orthophosphate in the recirculating water
  • mild steel (AISI-1010) corrosion rates average 15 mpy (381 microns py) with severe pitting corrosion present, and fouling of heat transfer surfaces in process equipment was a chronic problem.
  • the cooling system has a history of pH upsets and control problems which made corrosion and deposition control difficult.
  • the cooling system operate at a recirculation rate of 15,000 gpm (56,780 litres per minute) with an 18°F (10°C) temperature drop across the cooling tower.
  • Untreated well water was used as makeup to maintain the recirculating water at 2.5 cycles of concentration. Analysis of the recirculating water typically gave: 1230 ppm total hardness (as ppm CaC0 3 ), 740 ppm calcium hardness (as ppm CaC0 3 ), 40 ppm methyl orange alkalinity (as ppm CaC0 3 ), 34 ppm silica (as ppm, Si0 2 ) and 2360 micromhos conductivity.
  • composition of this invention applied at a concentration that would give 15 ppm AA/HPA polymer at 10 to 15 ppm orthophosphate was made to the cooling system, with the pH being controlled at 7. Over an 8-month period, mild steel corrosion rates were 1.9 mpy (48.3 pm py) without any significant pitting corrosion present. Additionally, no fouling problems were incurred with process equipment. Monitoring heat transfer coefficients (U) of a process exchanger indicated fouling had subsided after the application of the AA/HPA-phosphate treatment.
  • the addition of zinc was necessary because the phosphate/dispersant treatment alone was unable to establish an adequate diffusion barrier film in the low hardness water.
  • Mild steel corrosion rates were as high as 9 mpy (229 ⁇ m py), with pitting corrosion occasionally a problem.
  • the cooling system operated at a recirculation rate of 15,000 gpm (56,780 litres per minute) with an 8°F (4.4°C) temperature drop across the tower. River water was used as makeup to maintain the recirculating water at 1.5 cycles of concentration.
  • composition of this invention (applied at a concentration that would give 5 ppm AA/HPA polymer and 12 to 16 ppm orthophosphate in the recirculating water) eliminated the pitting corrosion and reduced mild steel corrosion rates to 1.4 mpy (35.6 pm py), without incurring any fouling problems.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (20)

1. Une composition pour former une pellicule protectrice d'oxyde passif à la surface d'une partie métallique ferreuse en contact avec une solution aqueuse, sans dépôt simultané d'incrustations ou tartre sur cette partie, ou avec peu d'un tel dépôt, composition qui comprend:
(a) un polymère hydrosoluble comprenant des motifs d'un acide acrylique ou d'un sel hydrosoluble de cet acide et des motifs d'un acrylate d'hydroxyalkyle inférieur, motifs qui ont les formules suivantes:
Figure imgb0076
formules dans lesquelles R représente l'hydrogène ou un alkyle en Ci à C3; R, représente OH, OM ou NH2, M étant un cation soluble dans l'eau; R2 est un alkylène en C2 à C6 et la rapport molaire x:y est compris entre 36:1 et 1:4; et
(b) un composé orthophosphorique soluble dans l'eau, le rapport pondéral du polymère au composé orthophosphorique exprimé en P04= étant compris entre 1:8 et 4:1, et cette composition ne contenant pas de zinc.
2. Composition selon la revendication 1 dans laquelle le rapport pondéral du polymère à l'orthophosphate (en P04=) est compris entre 1:6 et 2:1.
3. Composition selon la revendication 1 ou 2 qui contient en outre un composé d'acide organophosphonique soluble dans l'eau ou un sel hydrosoluble de cet acide.
4. Composition selon la revendication 3 dans laquelle le rapport pondéral de l'orthophosphate à l'acide phosphonique ou à son sel (les deux exprimés en P04=) est compris entre 1:2 et 13:1.
5. Composition selon la revendication 4 dans laquelle ce rapport est compris entre 2:1 et 8:1.
6. Composition selon l'une quelconque des revendications 1 à 5 dans laquelle, dans les formules indiquées, R représente l'hydrogène et R2 un alkylène à 3 atomes de carbone.
7. Composition selon l'une quelconque des revendications 1 à 6, qui contient également:
(c) un polyphosphate soluble dans l'eau.
8. Composition selon la revendication 7 dans laquelle le rapport pondéral de l'orthophosphate au polyphosphate (les deux exprimés en P04=) est compris entre 15:1 et 1:3.
9. Composition selon la revendication 8 dans laquelle ce rapport est compris entre 2,5:1 et 1:1.
10. Composition selon l'une quelconque des revendications 1 à 9, qui contient également un ou plusieurs inhibiteurs contre la corrosion du cuivre.
11. Composition selon la revendication 10 dans laquelle l'inhibiteur contre la corrosion du cuivre est choisi parmi des composés tolyltriazoliques, benzotriazoliques et benzothiazoliques.
12. Composition selon l'une quelconque des revendications 1 à 11 dans laquelle l'acrylate d'hydroxyalkyle est l'acrylate d'hydroxy-propyle.
13. Composition selon la revendication 12 dans laquelle le rapport des motifs d'acide acrylique aux motifs de l'acrylate d'hydroxypropyle est le rapport 3 et le copolymère a une masse moléculaire de 6000.
14. Composition selon la revendication 12 ou 13 dans laquelle l'acide organophosphonique ou son sel est l'acide hydroxy-éthylidène diphosphonique ou un sel hydrosoluble de cet acide.
15. Une méthode d'inhibition de la corrosion de parties métalliques ferreuses qui sont en contact avec une solution aqueuse ne contenant pas de zinc, sans qu'il se produise en même temps un dépôt d'incrustations ou tartre sur ces parties ferreuses, ou avec seulement un faible dépôt, inhibition qui est obtenue par la formation d'une pellicule protectrice d'oxyde passif sur la surface du métal en contact avec le milieu aqueux, méthode dans laquelle:
(1) on s'assure que le pH du milieu aqueux est d'au moins 5,5, ou plus;
(2) on s'assure que la teneur du milieu aqueux en ions calcium, nickel ou chrome ou mélanges de ces ions est d'au moins 15 parties par million de parties d'eau; et
(3) on ajoute au milieu aqueux une composition selon l'invention ou bien les composants de cette composition par des additions séparées, dans une ou des proportions suffisantes pour former sur la surface métallique une pellicule protectrice d'oxyde passif, pratiquement sans incrustations.
16. Méthode selon la revendication 15 dans laquelle l'orthophosphate (exprimé en P04=) est ajouté au milieu aqueux dans une proportion de 6 à 30 parties par million de parties d'eau, et le copolymère dans une proportion de 3 à 25 parties par million de parties d'eau.
17. Méthode selon la revendication 16 dans laquelle le pH est maintenu ou réglé entre 6,5 et 9,5.
18. Méthode selon la revendication 16 dans laquelle l'acide organophosphonique ou son sel (en P04=) est ajouté au milieu aqueux dans une proportion de 1 à 6 parties par million de parties d'eau.
19. Méthode selon l'une quelconque des revendications 15 à 18 dans laquelle le polyphosphate (en P04=) est ajouté au milieu aqueux dans une proportion de 3 à 10 parties par million de parties d'eau.
20. Méthode selon l'une quelconque des revendications 15 à 19 dans laquelle le milieu aqueux est celui d'un système d'eau de refroidissement.
EP80304433A 1979-12-10 1980-12-09 Procédé et composition pour l'inhibition de la corrosion Expired EP0033417B1 (fr)

Applications Claiming Priority (2)

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US06/101,658 US4303568A (en) 1979-12-10 1979-12-10 Corrosion inhibition treatments and method
US101658 1979-12-10

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BE (1) BE886589A (fr)
CA (1) CA1131436A (fr)
DE (1) DE3070746D1 (fr)
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IT (1) IT1134660B (fr)
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CA1131436A (fr) 1982-09-14
GB2066234B (en) 1983-11-16
IT8026551A0 (it) 1980-12-10
US4303568A (en) 1981-12-01
AU5845280A (en) 1981-06-18
GB2066234A (en) 1981-07-08
SG14988G (en) 1988-07-08
FR2482138A1 (fr) 1981-11-13
NZ193766A (en) 1983-03-15
FR2482138B1 (fr) 1986-05-09
AU532454B2 (en) 1983-09-29
IT1134660B (it) 1986-08-13
BE886589A (fr) 1981-04-01
DE3070746D1 (en) 1985-07-11
EP0033417A1 (fr) 1981-08-12

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